EP0428003A2 - Procédé de préparation de polyéther-glycols - Google Patents

Procédé de préparation de polyéther-glycols Download PDF

Info

Publication number: EP0428003A2
Authority: EP; European Patent Office
Prior art keywords: polymerization; thf; phase; ptmg; hydrocarbon
Prior art date: 1989-11-14
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.): Granted

Application number

EP90120770A

Other languages

German (de)

English (en)

Other versions

EP0428003B1 (fr

EP0428003A3 (en

Inventor

Herbert Dr. Mueller

Gerhard Dr. Jeschek

Rolf Dr. Fischer

Hans-Juergen Dr. Weyer

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

BASF SE

Original Assignee

BASF SE

Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)

1989-11-14

Filing date

1990-10-30

Publication date

1991-05-22

1990-10-30 Application filed by BASF SE filed Critical BASF SE

1991-05-22 Publication of EP0428003A2 publication Critical patent/EP0428003A2/fr

1991-10-16 Publication of EP0428003A3 publication Critical patent/EP0428003A3/de

1994-08-31 Application granted granted Critical

1994-08-31 Publication of EP0428003B1 publication Critical patent/EP0428003B1/fr

2010-10-30 Anticipated expiration legal-status Critical

Status Expired - Lifetime legal-status Critical Current

Links

238000000034 method Methods 0.000 title claims abstract description 21
238000002360 preparation method Methods 0.000 title claims abstract description 5
WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 82
229930195733 hydrocarbon Natural products 0.000 claims abstract description 21
150000002430 hydrocarbons Chemical class 0.000 claims abstract description 21
239000004215 Carbon black (E152) Substances 0.000 claims abstract description 17
YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 10
239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 8
150000002334 glycols Chemical class 0.000 claims abstract description 8
229920000570 polyether Polymers 0.000 claims abstract description 8
150000002924 oxiranes Chemical class 0.000 claims abstract description 6
238000006116 polymerization reaction Methods 0.000 claims description 32
239000003054 catalyst Substances 0.000 claims description 22
239000011964 heteropoly acid Substances 0.000 claims description 17
IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 11
XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 10
VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 7
TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 5
125000004432 carbon atom Chemical group C* 0.000 claims description 4
238000007334 copolymerization reaction Methods 0.000 claims description 3
125000001931 aliphatic group Chemical group 0.000 claims description 2
150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
230000000379 polymerizing effect Effects 0.000 abstract description 5
229920000642 polymer Polymers 0.000 description 26
BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 22
238000006243 chemical reaction Methods 0.000 description 11
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
239000000203 mixture Substances 0.000 description 7
239000000243 solution Substances 0.000 description 7
RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
-1 ether glycols Chemical class 0.000 description 6
229920001281 polyalkylene Polymers 0.000 description 6
239000002904 solvent Substances 0.000 description 5
GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
229910052710 silicon Inorganic materials 0.000 description 4
239000010703 silicon Substances 0.000 description 4
UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
239000002253 acid Substances 0.000 description 3
239000002585 base Substances 0.000 description 3
238000004140 cleaning Methods 0.000 description 3
238000009826 distribution Methods 0.000 description 3
238000005191 phase separation Methods 0.000 description 3
229920000909 polytetrahydrofuran Polymers 0.000 description 3
ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
229910052784 alkaline earth metal Inorganic materials 0.000 description 2
125000004429 atom Chemical group 0.000 description 2
229910052796 boron Inorganic materials 0.000 description 2
DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
230000000694 effects Effects 0.000 description 2
210000004177 elastic tissue Anatomy 0.000 description 2
238000004519 manufacturing process Methods 0.000 description 2
239000000178 monomer Substances 0.000 description 2
150000003839 salts Chemical class 0.000 description 2
VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
150000007513 acids Chemical class 0.000 description 1
239000003463 adsorbent Substances 0.000 description 1
239000003513 alkali Substances 0.000 description 1
150000001342 alkaline earth metals Chemical class 0.000 description 1
PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
150000008064 anhydrides Chemical class 0.000 description 1
229910052785 arsenic Inorganic materials 0.000 description 1
RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
230000015572 biosynthetic process Effects 0.000 description 1
BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
239000000292 calcium oxide Substances 0.000 description 1
ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
150000004649 carbonic acid derivatives Chemical class 0.000 description 1
230000015556 catabolic process Effects 0.000 description 1
230000003197 catalytic effect Effects 0.000 description 1
239000011951 cationic catalyst Substances 0.000 description 1
229910052804 chromium Inorganic materials 0.000 description 1
239000011651 chromium Substances 0.000 description 1
238000000576 coating method Methods 0.000 description 1
239000004035 construction material Substances 0.000 description 1
238000001816 cooling Methods 0.000 description 1
150000004292 cyclic ethers Chemical class 0.000 description 1
238000004042 decolorization Methods 0.000 description 1
230000001419 dependent effect Effects 0.000 description 1
238000010790 dilution Methods 0.000 description 1
239000012895 dilution Substances 0.000 description 1
238000004821 distillation Methods 0.000 description 1
150000002148 esters Chemical class 0.000 description 1
238000001914 filtration Methods 0.000 description 1
230000000887 hydrating effect Effects 0.000 description 1
150000004679 hydroxides Chemical class 0.000 description 1
WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
239000012535 impurity Substances 0.000 description 1
PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
239000000395 magnesium oxide Substances 0.000 description 1
CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
229910052751 metal Inorganic materials 0.000 description 1
239000002184 metal Substances 0.000 description 1
238000002156 mixing Methods 0.000 description 1
229910052750 molybdenum Inorganic materials 0.000 description 1
239000011733 molybdenum Substances 0.000 description 1
VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
238000006386 neutralization reaction Methods 0.000 description 1
229910052755 nonmetal Inorganic materials 0.000 description 1
TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
150000002926 oxygen Chemical class 0.000 description 1
PDDXOPNEMCREGN-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum;hydrate Chemical compound O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O PDDXOPNEMCREGN-UHFFFAOYSA-N 0.000 description 1
IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
229910052698 phosphorus Inorganic materials 0.000 description 1
239000011574 phosphorus Substances 0.000 description 1
238000000746 purification Methods 0.000 description 1
229910052711 selenium Inorganic materials 0.000 description 1
239000011669 selenium Substances 0.000 description 1
238000000926 separation method Methods 0.000 description 1
238000001179 sorption measurement Methods 0.000 description 1
239000007858 starting material Substances 0.000 description 1
238000003756 stirring Methods 0.000 description 1
229910052714 tellurium Inorganic materials 0.000 description 1
PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
229910052723 transition metal Inorganic materials 0.000 description 1
150000003624 transition metals Chemical class 0.000 description 1
WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
229910052721 tungsten Inorganic materials 0.000 description 1
239000010937 tungsten Substances 0.000 description 1
CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
230000007306 turnover Effects 0.000 description 1
229910052720 vanadium Inorganic materials 0.000 description 1
LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
239000008096 xylene Substances 0.000 description 1
229910052725 zinc Inorganic materials 0.000 description 1
239000011701 zinc Substances 0.000 description 1

Classifications

- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/16—Cyclic ethers having four or more ring atoms
- C08G65/20—Tetrahydrofuran

Definitions

This invention relates to a new process for the preparation of polyether glycols by polymerizing tetrahydrofuran or copolymerizing tetrahydrofuran with oxiranes in the presence of heteropolyacids and hydrocarbons.
Polyether glycols such as polyoxitetramethylene glycols (hereinafter referred to as “PTMG”), in particular polytetrahydrofuran (hereinafter referred to as “PTHF”) are important starting materials for the production of elastic fibers, elastic construction materials and coatings. They are prepared by polymerizing tetrahydrofuran (hereinafter referred to as “THF”) or by copolymerizing THF with oxiranes such as ethylene oxide or propylene oxide in the presence of cationic catalysts. According to EP-A-0 126 471, heteropolyacids are used as catalysts.
THF tetrahydrofuran
oxiranes such as ethylene oxide or propylene oxide
a process for the purification of PTMG solutions which are contaminated by heteropolyacids is described in EP-A-0 181 621.
the PTMG solutions in THF which are primarily obtained in the polymerization of THF and have a PTMG content of, for example, 23% by weight, are distilled to a concentration of about 50% in the first stage by distilling off unreacted THF .-% PTMG brought. Then add a substantial amount of a hydrocarbon, mix thoroughly and allow the mixture to settle in two phases for 30 hours.
the lower phase consists of 50% by weight of heteropolyacid, the rest of PTMG, THF and traces of the hydrocarbon.
the present invention was therefore based on the object of making the polymerization of THF with heteropolyacids more economical.
a possibility should be found to produce narrowly distributed polyalkylene ether glycols continuously.
the new process should also use less energy.
the polymerization rate and the polymerization conversion increase in the process according to the invention. This was unpredictable. Since the rate of polymerization is influenced by the monomer concentration, a slowdown in the polymerization should have been expected due to the dilution effect.
the polymerization of the THF is an equilibrium reaction that affects the tempera door-dependent final turnover determined. Build-up and breakdown in the reaction system are balanced. The conversion, based on the monomer used, should therefore be independent of a solvent present in the reaction system. Deviating from this expectation, however, we found that the polymerization and also the copolymerization of the THF in the solvent leads to a higher conversion than the polymerization in the absence of the solvent.
the polymerization of the THF or the copolymerization of the THF with oxiranes, such as ethylene oxide or propylene oxide with heteropolyacids as catalysts, is carried out in a manner known per se, as described, for. B. is described in EP-A 126 471.
Heteropolyacids which are used according to the invention are inorganic polyacids which, in contrast to isopolyacids, have at least two different central atoms.
Heteropolyacids arise from weak polybasic oxygen acids of a metal such as chromium, molybdenum, vanadium and tungsten as well as a non-metal such as arsenic, iodine, phosphorus, selenium, silicon, boron and tellurium as partially mixed anhydrides. Examples include dodecotungstophosphoric acid H3 [PW12O40] or dodecamolybdophosphoric acid H3 [PMO12O40].
the heteropolyacids can also contain actionoids or lantanoids as the second central atom (see Z. Chemie 17 (1977), pages 353 to 357 and 19 (1979), 308).
Phosphotungstic acid, phosphoromolybdic acid, silicon molybdic acid and silicon tungstic acid are particularly suitable catalysts for the process according to the invention.
1 molecule of heteropolyacid binds 20 to 40 molecules of water through a coordinative bond.
the heteropolyacids used as catalysts should contain about 1 to 8 molecules of water per molecule of heteropolyacid.
the water content in the heteropolyacid determines the molecular weight of the polymer obtained. The higher the water content in the catalyst, the lower the molecular weight of the polymer obtained.
the stated range of water content from 1 to 8 molecules per molecule of heteropolyacid corresponds to an average molecular weight of the polyether glycol of about 1000 to 3000.
hydrocarbons are used in amounts of 20 to 500, preferably 50 to 200,% by weight, based on the THF.
the polymerization is carried out continuously or batchwise, e.g. B. at temperatures from 20 to 100 ° C. At normal pressure you choose z. B. Temperatures of 30 to 65 ° C. If you polymerize under pressure, you choose z. B. Temperatures from 35 to 85 ° C.
the amount of catalyst is z. B. 20 to 300 parts by weight, based on 100 parts by weight of THF. It is expedient to use a polymerization reactor which is equipped with a mixing device, for. B. is equipped with a stirrer. Since the polymerization takes place in a 2-phase system, it is advantageous to use a phase separator in which the polymer solution separates from the catalyst phase. This lower catalyst phase is returned to the reaction as it occurs.
the upper phase of the phase separation vessel contains the resulting polymer, the hydrocarbon used as solvent, unreacted THF and heteropolyacid in the low concentration of e.g. B. 10 to 40 ppm.
This upper phase is now neutralized with a base.
base come e.g. B. the hydroxides and carbonates of the alkali or alkaline earth metals into consideration.
the PTMG obtained is freed from salt traces by filtration. It is often advisable to subject the polymer additionally to a hydrating catalytic decolorization on transition metal catalysts.
the new process gives the polyether glycols in a particularly economical manner.
the polymers surprisingly contain only traces of heteropolyacids, so that the process according to the invention considerably simplifies the process described in EP-A-181 621, which requires the multistage cleaning of the polymer solutions contaminated by heteropolyacids.
the concentration of heteropolyacids in the polymers which are obtained by the process of this invention is so low at 10 to 100 ppm that these proportions do not have to be returned to the polymerization batch.
the cost of the loss is negligible and the loss of activity in the polymerization reactor only becomes noticeable after a very long period of time.
the small amount of heteropolyacid dissolved in the polymer can be removed in a simple manner by neutralization with a base or adsorption as described in EP-A 0 181 621.
the complex separation of the main amount of heteropolyacid from the polymer batches described above on page 1, lines 30-40 is therefore not necessary in the process according to the invention.
the polyether glycols obtainable by the process according to the invention are distinguished by a very narrow molecular weight distribution and also outperform the polymers in this advantageous property, which are obtained by polymerizing THF in the absence of hydrocarbons.
the polymer phase has a PTMG content of 13% by weight.
the PTMG has a molecular weight of 2,410 and a heterogeneity quotient (Mw / Mn) of 1.8.
the heteropolyacid content in the polymer phase is 4.5% by weight.
the lower phase (catalyst phase) is placed in a polymerization reactor and 150 parts of THF, 0.75 parts of water and 100 parts of cyclohexane are added.
the polymerization is carried out at 60 ° C. for 5 hours with vigorous stirring.
the first batch provides 258 parts of the upper phase with a PTMG content of 37% by weight.
the PTMG has a molecular weight of 2050 and a heterogeneity quotient (Mw / Mn) of 1.5.
the separated upper phase contains approx. 28 ppm heteropoly acid.
the catalyst phase is returned to the reactor.
the polymerization apparatus is then operated continuously by adding 25 parts of THF with a water content of 0.43% by weight and 25 parts of cyclohexane per hour.
a mixture of the catalyst phase and the polymer phase enters the phase separation vessel.
the catalyst phase settles down. To the extent that it is obtained, it is returned to the polymerization reactor.
the upper polymer-containing phase is worked up.
the traces of heteropolyacid that are carried along are neutralized with dilute (10% by weight) sodium hydroxide solution and the polymer solution treated in this way is freed from solvents in two stages at normal pressure and at 10 mbar at temperatures up to 180.degree.
the polymer is filtered, for example, through a Seitz filter and a pure PTMG of very high quality standard with a heterogeneity ratio of 1.4 is obtained.
the degree of conversion of the polytetrahydrofuran in the continuous test, which is operated for a total of 72 hours, is 32% by weight.
the polymer has an average molecular weight of 1800, a heterogeneity quotient (Mw / Mn) of 1.6 and a propylene oxide content of approx. 30% by weight.

Landscapes

Chemical & Material Sciences (AREA)
Health & Medical Sciences (AREA)
Chemical Kinetics & Catalysis (AREA)
Medicinal Chemistry (AREA)
Polymers & Plastics (AREA)
Organic Chemistry (AREA)
Polyethers (AREA)
Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)

EP90120770A 1989-11-14 1990-10-30 Procédé de préparation de polyéther-glycols Expired - Lifetime EP0428003B1 (fr)

Applications Claiming Priority (2)

Application Number	Priority Date	Filing Date	Title
DE3937797		1989-11-14
DE3937797A DE3937797A1 (de)	1989-11-14	1989-11-14	Verfahren zur herstellung von polyetherglykolen

Publications (3)

Publication Number	Publication Date
EP0428003A2 true EP0428003A2 (fr)	1991-05-22
EP0428003A3 EP0428003A3 (en)	1991-10-16
EP0428003B1 EP0428003B1 (fr)	1994-08-31

Family

ID=6393471

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
EP90120770A Expired - Lifetime EP0428003B1 (fr)	1989-11-14	1990-10-30	Procédé de préparation de polyéther-glycols

Country Status (5)

Country	Link
US (1)	US5099074A (fr)
EP (1)	EP0428003B1 (fr)
JP (1)	JPH03168212A (fr)
DE (2)	DE3937797A1 (fr)
ES (1)	ES2057328T3 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
WO1996011221A1 (fr) *	1994-10-07	1996-04-18	Basf Aktiengesellschaft	Procede d'extraction des heteropolycomposes contenus dans des polyethers, polyesters et esters de polyethers
EP1219658A1 (fr) *	1999-08-19	2002-07-03	Asahi Kasei Kabushiki Kaisha	Polyoxytetramethylene-glycol et procede de production de ce compose

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
DE4108047A1 (de) *	1991-03-13	1992-09-17	Basf Ag	Verfahren zur einstellung des mittleren molekulargewichts von polyoxyalkylenglykolen und polyoxyalkylenderivaten bei der heteropolysaeure-katalysierten ringoeffnungspolymerisation von cyclischen ethern und(/oder acetalen
US5155283A (en) *	1991-03-19	1992-10-13	E. I. Du Pont De Nemours And Company	Polymerization of tetrahydrofuran using trifluoromethane sulfonic acid monohydrate as catalyst
US5648557A (en) *	1994-10-27	1997-07-15	Mobil Oil Corporation	Polyether lubricants and method for their production
US7169889B1 (en) *	1999-06-19	2007-01-30	Biocon Limited	Insulin prodrugs hydrolyzable in vivo to yield peglylated insulin
US6673889B1 (en) *	1999-06-28	2004-01-06	Omnova Solutions Inc.	Radiation curable coating containing polyfuorooxetane
EP1346726A4 (fr) *	2000-12-25	2004-09-15	Shiseido Co Ltd	Composition de parfum stimulant le systeme sympathique
US6867183B2 (en) *	2001-02-15	2005-03-15	Nobex Corporation	Pharmaceutical compositions of insulin drug-oligomer conjugates and methods of treating diseases therewith
US6835802B2 (en) *	2001-06-04	2004-12-28	Nobex Corporation	Methods of synthesizing substantially monodispersed mixtures of polymers having polyethylene glycol moieties
US6713452B2 (en)	2001-06-04	2004-03-30	Nobex Corporation	Mixtures of calcitonin drug-oligomer conjugates comprising polyalkylene glycol, uses thereof, and methods of making same
US6828305B2 (en) *	2001-06-04	2004-12-07	Nobex Corporation	Mixtures of growth hormone drug-oligomer conjugates comprising polyalkylene glycol, uses thereof, and methods of making same
US6828297B2 (en) *	2001-06-04	2004-12-07	Nobex Corporation	Mixtures of insulin drug-oligomer conjugates comprising polyalkylene glycol, uses thereof, and methods of making same
US6858580B2 (en)	2001-06-04	2005-02-22	Nobex Corporation	Mixtures of drug-oligomer conjugates comprising polyalkylene glycol, uses thereof, and methods of making same
US7713932B2 (en) *	2001-06-04	2010-05-11	Biocon Limited	Calcitonin drug-oligomer conjugates, and uses thereof
US7196059B2 (en) *	2001-09-07	2007-03-27	Biocon Limited	Pharmaceutical compositions of insulin drug-oligomer conjugates and methods of treating diseases therewith
WO2003105768A2 (fr) *	2002-06-13	2003-12-24	Nobex Corporation	Methodes de reduction du nombre et de la gravite des episodes hypoglycemiques dans le traitement du diabete sucre
US20060182692A1 (en)	2003-12-16	2006-08-17	Fishburn C S	Chemically modified small molecules
ES2445585T3 (es) *	2003-12-16	2014-03-04	Nektar Therapeutics	Composiciones monodispersas de naloxol PEGilado
KR100914055B1 (ko) *	2007-09-11	2009-08-28	주식회사 효성	폴리테트라메틸렌 에테르 글리콜에서 올리고머의 제거 방법
JP5744841B2 (ja) *	2009-04-15	2015-07-08	インヴィスタテクノロジーズエスアエルエル	コポリエーテルグリコールの製法
CN103890068A (zh) *	2012-07-02	2014-06-25	因温斯特北美公司	四氢呋喃清洗处理方法
CN113563575B (zh) *	2021-07-29	2023-04-28	浙江皇马科技股份有限公司	一种环氧烷烃-四氢呋喃共聚物及制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US3478109A (en) *	1967-07-28	1969-11-11	Eastman Kodak Co	Solvent extraction of polymeric glycols using methanol
EP0153794A1 (fr) *	1984-01-09	1985-09-04	E.I. Du Pont De Nemours And Company	Procédé pour réduire la teneur d'éthers cycliques oligomères dans un polymérisat
EP0181621A2 (fr) *	1984-11-13	1986-05-21	Asahi Kasei Kogyo Kabushiki Kaisha	Procédé de purification d'éther de polyalkylène

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
CA1216597A (fr) *	1983-05-23	1987-01-13	Atsushi Aoshima	Production de polyetherglycole
US4658065A (en) *	1984-03-28	1987-04-14	Asahi Kasei Kogyo Kabushiki Kaisha	Process for producing polyether polyol and a product
DE3514547A1 (de) *	1985-04-23	1986-10-23	Basf Ag, 6700 Ludwigshafen	Verfahren zur verminderung des anteils von cyclischen oligomeren ethern in polytetramethylenetherglykolen oder polyoxibutylen-polyoxialkylenglykolen
DE3607946A1 (de) *	1986-03-11	1987-09-17	Basf Ag	Verfahren zur einengung der molekulargewichtsverteilung von polytetrahydrofuran und von copolymerisaten aus tetrahydrofuran und alkylenoxiden

1989
- 1989-11-14 DE DE3937797A patent/DE3937797A1/de not_active Withdrawn
1990
- 1990-10-26 US US07/603,519 patent/US5099074A/en not_active Expired - Lifetime
- 1990-10-30 EP EP90120770A patent/EP0428003B1/fr not_active Expired - Lifetime
- 1990-10-30 ES ES90120770T patent/ES2057328T3/es not_active Expired - Lifetime
- 1990-10-30 DE DE59006970T patent/DE59006970D1/de not_active Expired - Lifetime
- 1990-11-06 JP JP2299096A patent/JPH03168212A/ja active Pending

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US3478109A (en) *	1967-07-28	1969-11-11	Eastman Kodak Co	Solvent extraction of polymeric glycols using methanol
EP0153794A1 (fr) *	1984-01-09	1985-09-04	E.I. Du Pont De Nemours And Company	Procédé pour réduire la teneur d'éthers cycliques oligomères dans un polymérisat
EP0181621A2 (fr) *	1984-11-13	1986-05-21	Asahi Kasei Kogyo Kabushiki Kaisha	Procédé de purification d'éther de polyalkylène

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
WO1996011221A1 (fr) *	1994-10-07	1996-04-18	Basf Aktiengesellschaft	Procede d'extraction des heteropolycomposes contenus dans des polyethers, polyesters et esters de polyethers
CN1071345C (zh) *	1994-10-07	2001-09-19	巴斯福股份公司	从聚醚、聚酯和聚醚酯中分离杂多化合物的方法
EP1219658A1 (fr) *	1999-08-19	2002-07-03	Asahi Kasei Kabushiki Kaisha	Polyoxytetramethylene-glycol et procede de production de ce compose
EP1219658A4 (fr) *	1999-08-19	2002-11-13	Asahi Chemical Ind	Polyoxytetramethylene-glycol et procede de production de ce compose

Also Published As

Publication number	Publication date
JPH03168212A (ja)	1991-07-22
ES2057328T3 (es)	1994-10-16
EP0428003B1 (fr)	1994-08-31
DE3937797A1 (de)	1991-05-16
US5099074A (en)	1992-03-24
DE59006970D1 (de)	1994-10-06
EP0428003A3 (en)	1991-10-16

Publication	Publication Date	Title
EP0428003B1 (fr)	1994-08-31	Procédé de préparation de polyéther-glycols
EP0003112B1 (fr)	1982-06-02	Procédé de préparation de diester d'acide carboxylique de polybutylène-glycol par polymérisation du tétrahydrofurane prétraité chimiquement
DE69030776T2 (de)	1997-09-11	Wiedergewinnung von Doppelmetallcyanidkomplexkatalysatoren aus Polymeren
EP0782594B1 (fr)	1998-08-12	Procede de fabrication de polytetrahydrofurane
EP1141083B1 (fr)	2004-08-18	Procede permettant de produire des polyols hautement ramifies a partir de glycidol
EP0421268B1 (fr)	1995-01-18	Procédé pour la purification de glycols polyalkylène éthers contenant des hétéropolyacides
DE1111398B (de)	1961-07-20	Verfahren zur Herstellung von Epoxypolybutadien
DE1199001B (de)	1965-08-19	Verfahren zur Polymerisation von Olefinoxyden
DE10239947A1 (de)	2004-03-11	Verfahren zur Herstellung von Tetrahydrofuran-Copolymeren
DE69112528T2 (de)	1996-04-04	Entfernung von Hydrierkatalysatoren aus Polymerlösungen durch katalytische Präzipitation.
DE4421788C2 (de)	2000-04-27	Verfahren zur Herstellung eines Polyalkylenethers mit Ester-Endkappen
DE2760272C2 (de)	1987-04-16	Verfahren zur Herstellung von Poly-(tetramethylenether)-glykol durch Alkoholyse eines Ester-Endgruppen aufweisenden Poly-(tetramethylenether)-glykols
EP0648784B1 (fr)	1997-01-02	Procédé de préparation de polymères téléchéliques
DE69920374T2 (de)	2005-06-30	Verfahren zur herstellung von polytetrahydrofuran
EP1539854B1 (fr)	2006-04-26	Procede de production de mono- et de diesters de polytetrahydrofurane et de copolymeres de tetrahydrofurane
EP0784643B1 (fr)	1998-06-17	Procede d'extraction des heteropolycomposes contenus dans des polyethers, polyesters et esters de polyether
DE4325023A1 (de)	1995-02-02	Verfahren zur Herstellung von Polytetrahydrofuran oder Tetrahydrofuran-Alkylenoxid-Copolymeren
EP1576030B1 (fr)	2006-05-03	Procede de production de copolymeres de tetrahydrofurane
EP1613684B1 (fr)	2006-06-28	Procede de production de copolymeres de tetrahydrofurane
EP0784642B1 (fr)	1999-03-10	Procede d'extraction des heteropolycomposes contenus dans des polyethers, polyesters et esters de polyethers
DE10210728A1 (de)	2003-10-02	Verfahren zur Herstellung von Polytetrahydrofuran mit vermindertem Gehalt an oligomeren cyclischen Ethern
DE2711915C2 (fr)	1988-02-25
DE1937728C (de)	1973-01-18	Verfahren zur Polymerisation von Alkylenoxyden
DD220608A1 (de)	1985-04-03	Verfahren zur herstellung von polyetheralkoholen
DE10210727A1 (de)	2003-10-02	Verfahren zur Verminderung des Anteils an cyclischen oligomeren Ethern in Polytetrahydrofuran oder Copolymeren aus Tetrahydrofuran

Legal Events

Date	Code	Title	Description
1991-04-05	PUAI	Public reference made under article 153(3) epc to a published international application that has entered the european phase	Free format text: ORIGINAL CODE: 0009012
1991-05-22	17P	Request for examination filed	Effective date: 19901227
1991-05-22	AK	Designated contracting states	Kind code of ref document: A2 Designated state(s): BE DE ES FR GB IT NL
1991-08-29	PUAL	Search report despatched	Free format text: ORIGINAL CODE: 0009013
1991-10-16	AK	Designated contracting states	Kind code of ref document: A3 Designated state(s): BE DE ES FR GB IT NL
1994-03-16	17Q	First examination report despatched	Effective date: 19940127
1994-07-15	GRAA	(expected) grant	Free format text: ORIGINAL CODE: 0009210
1994-08-31	AK	Designated contracting states	Kind code of ref document: B1 Designated state(s): BE DE ES FR GB IT NL
1994-10-06	REF	Corresponds to:	Ref document number: 59006970 Country of ref document: DE Date of ref document: 19941006
1994-10-13	ITF	It: translation for a ep patent filed
1994-10-16	REG	Reference to a national code	Ref country code: ES Ref legal event code: FG2A Ref document number: 2057328 Country of ref document: ES Kind code of ref document: T3
1994-10-19	GBT	Gb: translation of ep patent filed (gb section 77(6)(a)/1977)	Effective date: 19940920
1995-01-13	ET	Fr: translation filed
1995-07-01	PLBE	No opposition filed within time limit	Free format text: ORIGINAL CODE: 0009261
1995-07-01	STAA	Information on the status of an ep patent application or granted ep patent	Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT
1995-08-23	26N	No opposition filed
2002-01-01	REG	Reference to a national code	Ref country code: GB Ref legal event code: IF02
2004-10-03	PGFP	Annual fee paid to national office [announced via postgrant information from national office to epo]	Ref country code: NL Payment date: 20041003 Year of fee payment: 15
2004-10-08	PGFP	Annual fee paid to national office [announced via postgrant information from national office to epo]	Ref country code: FR Payment date: 20041008 Year of fee payment: 15
2004-10-27	PGFP	Annual fee paid to national office [announced via postgrant information from national office to epo]	Ref country code: GB Payment date: 20041027 Year of fee payment: 15
2004-10-28	PGFP	Annual fee paid to national office [announced via postgrant information from national office to epo]	Ref country code: DE Payment date: 20041028 Year of fee payment: 15
2004-11-16	PGFP	Annual fee paid to national office [announced via postgrant information from national office to epo]	Ref country code: ES Payment date: 20041116 Year of fee payment: 15
2004-12-15	PGFP	Annual fee paid to national office [announced via postgrant information from national office to epo]	Ref country code: BE Payment date: 20041215 Year of fee payment: 15
2005-10-30	PG25	Lapsed in a contracting state [announced via postgrant information from national office to epo]	Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20051030 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20051030
2005-10-31	PG25	Lapsed in a contracting state [announced via postgrant information from national office to epo]	Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20051031 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20051031
2005-12-03	PG25	Lapsed in a contracting state [announced via postgrant information from national office to epo]	Ref country code: DE Free format text: LAPSE BECAUSE OF THE APPLICANT RENOUNCES Effective date: 20051203
2006-05-01	PG25	Lapsed in a contracting state [announced via postgrant information from national office to epo]	Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20060501
2006-06-28	GBPC	Gb: european patent ceased through non-payment of renewal fee	Effective date: 20051030
2006-06-30	PG25	Lapsed in a contracting state [announced via postgrant information from national office to epo]	Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20060630
2006-07-03	NLV4	Nl: lapsed or anulled due to non-payment of the annual fee	Effective date: 20060501
2006-10-20	REG	Reference to a national code	Ref country code: FR Ref legal event code: ST Effective date: 20060630
2007-01-16	REG	Reference to a national code	Ref country code: ES Ref legal event code: FD2A Effective date: 20051031
2007-12-31	BERE	Be: lapsed	Owner name: BASF A.G. Effective date*: 20051031